CN109796463A - A kind of synthesis and application of the hypochlorous ratio type fluorescence probe of identification with two-phpton property - Google Patents
A kind of synthesis and application of the hypochlorous ratio type fluorescence probe of identification with two-phpton property Download PDFInfo
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- CN109796463A CN109796463A CN201910039026.XA CN201910039026A CN109796463A CN 109796463 A CN109796463 A CN 109796463A CN 201910039026 A CN201910039026 A CN 201910039026A CN 109796463 A CN109796463 A CN 109796463A
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- 239000000523 sample Substances 0.000 title claims abstract description 49
- 230000015572 biosynthetic process Effects 0.000 title claims description 4
- 238000003786 synthesis reaction Methods 0.000 title claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 61
- 230000004044 response Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 208000027418 Wounds and injury Diseases 0.000 abstract 1
- 230000006378 damage Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000002189 fluorescence spectrum Methods 0.000 abstract 1
- 208000014674 injury Diseases 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000252212 Danio rerio Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010056677 Nerve degeneration Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 210000005007 innate immune system Anatomy 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to the preparations and application of a kind of ratio type fluorescence probe for detecting hypochlorous acid (HClO) of tool two-phpton property, belong to chemical analysis detection technique field.Its molecular structure is as follows:The probe molecule maximum emission wavelength at fluorescence spectrum red shift to 650nm, realizes ratio feux rouges and quickly detects hypochlorous acid (HClO), improve the sensitivity of detection after 583nm, probe molecule and hypochlorous acid (HClO) effect；The light injury of background fluorescence and living cells of the launch wavelength during red light wavelength region can reduce probe in detecting, penetration capacity of the enhancing biology to tissue.Probe molecule of the present invention has good linear in certain time and concentration range, it is strong to hypochlorous acid (HClO) recognition capability, the good, strong antijamming capability of selectivity, fast response time, such probe have important application value in fields such as biochemistries.
Description
Technical field
The invention belongs to chemical analysis detection technique fields, and in particular to a kind of detection hypochlorous acid with two-phpton property
(HClO) preparation of novel ratio type fluorescence probe and its application in terms of detecting hypochlorous acid (HClO).
Background technique
Active oxygen (ROS) is the important and universal compound of one kind present in biosystem, it is in various physiology and disease
It is played a crucial role during reason, oxidative stress is generated, so as to cause disease caused by oxidative damage, hypochlorous acid (HClO)
With its conjugate base (OCl-) universal generally existing as one of important active oxygen.Due to secondary chlorine in natural system
Acid sterilizing ability and as important antibacterials, for biologically, low chloric acid can be killed in innate immune system
Pathogen, because of its anti-microbial property.According to studies have shown that suitable hypochlorous acid (HClO) by hydrogen peroxide (H2O2) and chlorine from
Sub (Cl-) is generated by enzyme myeloperoxidase enzyme (MPO) catalysis reaction, to be conducive to normal physiological activity.However, excessive
Hypochlorite and many diseases have close relationship, such as cardiovascular disease, arthritis, nerve degeneration and cancer.Therefore, having must
A kind of effective method is developed to detect hypochlorous acid, to assist clinical treatment.
Summary of the invention
It is an object of the present invention to provide a kind of fluorescence probe synthetic methods of simple and effective；Another object of the present invention
It is good to be to provide a kind of selectivity, strong antijamming capability has ratio red light emission wavelength, and energy rapid sensitive is realized to hypochlorous acid
(HClO) fluorescence probe detected.
The present invention solves the problems, such as that the technical solution taken is, a kind of ratio type identification hydrogen peroxide novel fluorescence probe,
Molecular structural formula is as follows:
Synthetic route is as follows:
Specific synthetic method is as follows: (a) by compound TQL (117mg, 0.5mmol)) and ethyl acetoacetate (130mg,
2.0mL dehydrated alcohol 1.0mmol) is dissolved in reaction flask, piperidines (10.0 μ L) is added, 2h is stirred at room temperature.It is precipitated in reaction process big
Red solid is measured, stops reaction and filters, filter cake is washed with methylene chloride, obtains pure product TQC (130mg, 87% yield).
(b) TQC (200mg, 0.67mmol) is dissolved in anhydrous methylene chloride (15mL), addition 2 mercapto ethanol (100mg,
1.2mmol) and 250 μ L of methanesulfonic acid, back flow reaction 5 hours.Then stop reaction concentration of reaction solution, it is solid that column chromatography for separation obtains yellow
The compound TQC-HClO (60mg, 25% yield) of body.
The mechanism of action of fluorescence probe of the invention is as follows, and probe molecule has the fluorescence of strong electron-donating group by introducing
Parent TQL enhances intramolecular ICT effect, shows big Stokes shift and high quantum efficiency.Hypochlorous acid (HClO)
Can in oxidised probe molecule ketal moieties sulfydryl, release dyestuff TQC, further strengthen intramolecular ICT process and cause
Launch wavelength red shift and emit feux rouges (650nm), to achieve the purpose that specific detection hypochlorous acid (HClO).Probe molecule
Response process is as follows:
Fluorescence probe of the invention has ratio fluorescent emission, and transmitting yellow fluorescence exists before acting on hypochlorous acid (HClO)
At 583nm, red-shifted emission peak occurs for fluorescence at 650nm after effect.
Probe molecule of the present invention has two-phpton property, there is long ratio to emit hypochlorous acid (HClO) response
Wavelength emits red shift after response and red fluorescence is presented and has good selectivity to other substances and anti-interference ability,
And the sensitivity having had has wider application range.For long ratio transmitted wave with strong tissue penetration, this is glimmering
Light probe has potential application in biology with fields such as chemistry.
Detailed description of the invention
Fig. 1 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3CN30% is molten
In liquid, with the UV absorption variation diagram before and after hypochlorous acid (HClO) effect, abscissa is wavelength, and ordinate is respectively to absorb by force
Degree.
Fig. 2 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
Ultraviolet spectrogram be added hypochlorous acid (HClO) amount variation, abscissa is wavelength, and ordinate is respectively absorption intensity.
Fig. 3 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
The fluorogram variation before and after hypochlorous acid (HClO) is added, abscissa is wavelength, and ordinate is fluorescence intensity.
Fig. 4 is dyestuff TQC (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
It absorbs and transmitting map, abscissa is wavelength, ordinate is absorbing/fluorescent intensity.
Fig. 5 is the solid fluorescence phenomenon of fluorescence probe of the invention, and left figure is the situation under natural lighting, and right figure is
The solid fluorescence of green is presented in situation of the portable ultraviolet lamp of 365nm according under.
Fig. 6 is the Solid fluorescene spectrum figure of fluorescence probe of the invention, and abscissa is wavelength, and ordinate is fluorescence intensity.
Fig. 7 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
With the fluorogram variation diagram for the amount that hypochlorous acid (HClO) is added, abscissa is wavelength, and ordinate is fluorescence intensity.
Fig. 8 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
As the fluorescence intensity ratio for the amount that hypochlorous acid (HClO) is added changes scatter plot, abscissa is hypochlorous acid (HClO) concentration, is indulged
Coordinate is fluorescence intensity ratio.
Fig. 9 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
The amount of hypochlorous acid (HClO) and the linear relationship of fluorescence intensity ratio variation is added, abscissa is hypochlorous acid concentration, and ordinate is
Fluorescence intensity ratio.
Figure 10 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
After 28 times of single amounts hypochlorous acid (HClO) are added, fluorescence intensity ratio is with the variation of time, and abscissa is the time, and ordinate is glimmering
Intensity ratio.
Figure 11 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) exist and be not present hypochlorous acid (HClO) when
Fluorescence intensity ratio changes in the system of different pH value, and abscissa is pH value, and ordinate is fluorescence intensity ratio.
Figure 12 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
There are fluorescent emission situation when hypochlorous acid (HClO) and other substances, abscissa is wavelength, and ordinate is fluorescence intensity.
Figure 13 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
In the presence of (PBS, ClO-,1O2,NO·,ROO·,H2O2,TBHP,·OH,ONOO-,Al3+,Ca2+,Fe3+,Mg2+,Zn2+,Cl-,I-,
F-,Br-,CO3 2-,NO3-) etc. different materials when selectivity bar chart, ordinate I650/I583The variation of intensity.
Figure 14 is fluorescence probe (10.0 × 10 of the invention-6Mol/L) in PBS (10mM, pH=7.4)/CH3In CN30%
In the presence of (PBS, ClO-,1O2,NO·,ROO·,H2O2,TBHP,·OH,ONOO-,Al3+,Ca2+,Fe3+,Mg2+,Zn2+,Cl-,I-,
F-,Br-,CO3 2-,NO3-) etc. it is different when interfering bar chart, ordinate I650/I583The variation of intensity.
Figure 15 is fluorescence probe of the invention in PBS (10mM, pH=7.4)/CH3In CN30%, at distance 20cm with
After 500W xenon lamp irradiates 1 hour, the variation of ultra-violet absorption spectrum, abscissa is wavelength, and ordinate is absorption intensity.
Figure 16 is fluorescence probe of the invention in PBS (10mM, pH=7.4)/CH3In CN30%, at distance 20cm with
After 500W xenon lamp irradiates 1 hour, the scatter plot that UV absorption changes over time, abscissa is the time, and ordinate is absorption intensity.
Figure 17 is that the toxicity research of fluorescence probe cell applicability of the invention is tested, and abscissa is concentration and probe concentration, indulges and sits
It is designated as cell survival rate.
Figure 18 is that two photon absorption cross section measures under fluorescence probe difference excitation wavelength of the invention, and abscissa is excitation wave
Long, ordinate is two photon absorption cross section.
Figure 19 is the intracellular two photon imaging of fluorescence probe of the invention.
Figure 20 is that fluorescence probe and hypochlorous acid (HClO) Response Mechanism of the invention are verified.
Figure 21 is that fluorescence probe of the invention detects hypochlorous acid (HClO) into the cell.
Figure 22 is to detect hypochlorous acid (HClO) in fluorescence probe zebra fish of the invention.
Example is embodied
Embodiment 1: the synthesis of probe molecule
TQC (200mg, 0.67mmol) is dissolved in anhydrous methylene chloride (15mL), addition 2 mercapto ethanol (100mg,
1.2mmol) and 250 μ L of methanesulfonic acid, back flow reaction 5 hours.Then stop reaction reaction solution is concentrated, column chromatography for separation obtains yellow
The compound TQC-HClO (60mg, 25% yield) of color solid.HRMS(ESI)m/z:[M+Na]+calcdforC19H24N2NaO3S+,383.13998；found,383.13984.1H NMR(400MHz,CDCl3) δ 7.62 (s, 1H), 6.48 (d, J=19.4Hz,
2H),4.37-4.42(m,5.2Hz,1H),4.20–4.10(m,1H),3.55–3.44(m,2H),3.43–3.29(m,4H),
3.26 (s, 2H), 3.17-3.11 (m, 1H), 2.99-2.94 (m, 4.9Hz, 1H), 1.95 (s, 3H), 1.20 (q, J=6.8Hz,
6H).13C NMR(100MHz,CDCl3)δ161.5,149.2,139.7,134.5,125.6,108.4,107.1,96.2,92.1,
71.1,47.0,45.7,45.5,45.4,45.2,33.33,29.6,10.2,9.9.
Embodiment 2: the application of fluorescence probe of the invention
Probe molecule is dissolved in PBS (10mM, pH=7.4)/CH310.0 × 10 are configured in CN30%-6Mol/L's is molten
Various substance (PBS, ClO are added into solution for liquid-,1O2,NO·,ROO·,H2O2,TBHP,·OH,ONOO-,Al3+,Ca2+,
Fe3+,Mg2+,Zn2+,Cl-,I-,F-,Br-,CO3 2-,NO3-) after do not cause the significant change of probe emission peak itself, when secondary chlorine
Sour (HClO) and interfering substance (PBS, ClO-,1O2,NO·,ROO·,H2O2,TBHP,·OH,ONOO-,Al3+,Ca2+,Fe3+,
Mg2+,Zn2+,Cl-,I-,F-,Br-,CO3 2-,NO3-) when coexisting, can occur to respond and the transmitting of itself is caused to disappear and occur
Red shift generates new emission peak, and the influence of the interference-free factor of probe shows very strong anti-interference ability.The probe molecule
Hypochlorous acid (HClO) can be quickly detected, a fast speed of response is shown.Show to visit by photo and thermal stability experiment
The photo and thermal stability that needle set has had, cytotoxicity experiment illustrate that the biology that probe has had is applicable in prospect, realize internal hypochlorous acid
(HClO) detection and two photon imaging.
Claims (1)
1. one kind has the synthesis of the ratio type fluorescence probe of two-phpton property identification hypochlorous acid (HClO), structure is as follows:
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| CN201910039026.XA CN109796463B (en) | 2019-01-16 | 2019-01-16 | Synthesis and application of ratio type fluorescent probe with two-photon property and capable of identifying hypochlorous acid |
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| CN201910039026.XA CN109796463B (en) | 2019-01-16 | 2019-01-16 | Synthesis and application of ratio type fluorescent probe with two-photon property and capable of identifying hypochlorous acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818734A (en) * | 2019-10-23 | 2020-02-21 | 中南大学 | Fluorescent probe with double-ratio recognition function for hydrogen peroxide and hypochlorous acid |
| CN113880821A (en) * | 2021-10-29 | 2022-01-04 | 南京碳硅人工智能生物医药技术研究院有限公司 | Design and synthesis method of fluorescent probe for imaging epileptic intracerebral hypochlorous acid characteristics by two-photon fluorescent probe |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106749292A (en) * | 2016-11-30 | 2017-05-31 | 中南大学 | A kind of preparation and application of hypochlorous acid fluorescence probe |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818734A (en) * | 2019-10-23 | 2020-02-21 | 中南大学 | Fluorescent probe with double-ratio recognition function for hydrogen peroxide and hypochlorous acid |
| CN113880821A (en) * | 2021-10-29 | 2022-01-04 | 南京碳硅人工智能生物医药技术研究院有限公司 | Design and synthesis method of fluorescent probe for imaging epileptic intracerebral hypochlorous acid characteristics by two-photon fluorescent probe |
| CN113880821B (en) * | 2021-10-29 | 2024-03-12 | 南京碳硅人工智能生物医药技术研究院有限公司 | Fluorescent probe design for epileptic intracerebral hypochlorous acid characteristic imaging by two-photon fluorescent probe and synthetic method thereof |
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